Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
  • C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
  • C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
  • C07C225/30—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by two rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/07—Optical isomers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
  • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
  • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
  • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

• R is hydrogen, halogen or lower alkoxy and R is selected from radicals represented by the formulae Ljm V VI
• R is hydrogen, lower alkyl, phenyl, substituted phenyl and phenyl-lower alkyl; as well as a process for their preparation.
• lower alkyl indicates straight or branched chain alkyl groups containing from one to seven carbon atoms such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, ter. butyl, amyl, hexyl and heptyl.
• the terminology lower alkoxy indicates those alkoxy radicals having from one to four carbon atoms such as, for example, methoxy, ethoxy, propyloxy, butyloxy and the like.
• R is a substituted phenyl radical, said substitutents are selected from the group consisting of halogen, preferably chlorine 3,729,492 Patented Apr.
• R is phenyl lower alkyl
• the alkyl portion thereof contains from one to four carbon atoms.
• a preferred phenyl lower alkyl group is 2-phenylethyl.
• compounds represented by Formula I may be prepared by reacting a compound represented by the formula wherein R is as previously defined and R is hydrogen or a leaving group, with an amine represented by the formula R NH: III
• the expression leaving group represents a group replaceable by an amino group such as, for example, acyloxy such as, acetoxy, propionoxy and the like; alkoxy such as methoxy, ethoxy and the like; aryloxy such as phenyloxy; aralkoxy such as benzyloxy and the like; arylsulfonyloxy such as tosyloxy and the like; alkylsulfonyloxy such as mesyloxy; arylthio; aralkylthio; hydroxy; halogen such as bromine or chlorine and the like.
• an amino group such as, for example, acyloxy such as, acetoxy, propionoxy and the like; alkoxy such as methoxy, ethoxy and the like; aryloxy such as phenyloxy; aralkoxy such as benzyloxy and the like; arylsulfonyloxy such as tosyloxy and the like; alkylsul
• the reaction of the compounds represented by Formula II with the amines represented by Formula III is expediently carried out in a suitable organic solvent.
• suitable organic solvents include, for example, alcohols such as methanol, ethanol and the like; aliphatic hydrocarbons; halogenated aliphatic hydrocarbons such as methylene chloride; aromatic hydrocarbons such as benzene; nitrobenmne; dioxan; tetrahydrofuran; dirnethylformamide, and the like.
• the reaction is carried out at a temperature of from about room temperature to about 150 C., preferably at a temperature of from about 60 to C.
• an excess of amine of Formula III is utilized to bind acid which is possibly released.
• an organic amine which is otherwise inert under the reaction conditions can also be utilized.
• Suitable amines include, for example, triethylamine, pyridine and the like.
• the compounds represented by Formula I may be prepared by oxidizing a compound represented by the formula wherein R and R are as defined above.
• the oxidation reaction may be carried out in a conventional manner such as, for example, by passing oxygen or air through the reaction solution, or by treatment with dilute hydrogen peroxide or a ferric iron salt or the like.
• the compounds represented by Formula I wherein R is hydrogen or a halogen other than chlorine may be, if desired, converted to the corresponding compound wherein R is chlorine by heating in a suitable inert solvent with, for example, lithium chloride or by passing chlorine gas through the reaction mixture.
• This reaction is expediently effected at a temperature of from about 3 50 C. to about 150 C., preferably from about 80 C. to about 120 C.
• the reduction is acomplished by known methods, for example, catalytic hydrogenation by for example platinum in glacial acetic acid, Raney-nickel in alcoholic ammonia and the like, or by chemical reduction, for example, treatment with sodium in alcohol, zinc in acetic acid, lithium aluminum hydride in ether and the like.
• the compounds represented by Formula III occur in one or both of two stereo-isomeric forms, i.e., the exo and endo forms. Which of these forms predominates in the product depends on the method of reduction. Thus, reduction with sodium in alcohol yields predominately the endo form, reduction with lithium aluminum hydride yields practically pure exo form and catalytic hydrogenation yields a mixture of exo and endo in a proportion of about 3:7.
• optical antipodes and racemic mixtures of the starting compounds give rise to the corresponding antipodes or racemic mixtures of the final product.
• a mixture of the two stereoisomeric forms can be separated from each other in a known manner, such as, for example, on the basis of the dilferent rates of crystallization of different salts, i.e., by fractional crystallization, especially of the acetates.
• the compounds represented by Formula III are bases and can be converted, if desired, into acid addition salts.
• Suitable acids include, for example, inorganic acids such as hydrochloric acid, hydrohromic acid, sulphuric acid,
• phosphoric acid and the like and organic acids such as, for example, acetic acid, tartaric acid, maleic acid, fumaric acid, citric acid, oxalic acid, toluenesulphonic acid and the like.
• the oxime compounds represented by Formula VII are likewise new compounds with the exception of those compounds wherein R, is hydrogen, methyl, propyl or unsubstituted phenyl,
• the compounds represented by Formula VII can be prepared, for example, by heating a compound represented by the formula R: VIII wherein R is as defined above with, for example, hydroxylamine hydrochloride and sodium ethylate in ethanol.
• the compounds represented by Formula VIII are likewise new compounds with the exception of those wherein R is hydrogen, methyl, ethyl, propyl, phenyl and substituted phenyl.
• the compounds represented by Formula VIII wherein R is as defined above, excluding hydrogen, may be prepared starting with camphor, by reaction with an organometallic compound selected from those represented by the formulae wherein R is methyl, phenyl, substituted phenyl, or benzyl, R is a lower alkyl of l-4 carbons, R2, is hydrogen or a lower alkyl of 1-5 carbons, phenyl or phenyl lower alkyl having 1-2 carbons in the aliphatic portion, Me is selected from the group consisting of sodium, potassium, lithium or MgX and X is halogen; and the reaction product hydrolyzed.
• the hydrolysis product may then, optionally, be hydrogenated on the existing available double or triple bonds and, if desired, dehydrated.
• the product is then reacted with a cyano compound to form the corresponding exo-acid amide [Ritter-Reaction: Org. Reactions: vol. 17, 213-325 (1969)].
• the exo-acid amides are then treated in a known manner to hydrolyze to the corresponding exo-amine, such as by heating with an acid or base, preferably with an acid, expediently at the reflux temperature of the reaction mixture.
• exo-amine is then dehydrogenated to the corresponding imine such as, for example, by treatment with t-butyl hypochlorite in an inert organic solvent such as, for example, ether, to form the corresponding N-chlorocompound and treatment of this compound with an organic or inorganic base such as, for example, sodium ethoxide.
• an organic or inorganic base such as, for example, sodium ethoxide.
• the imine is finally hydrolyzed in a known manner to form compounds represented by Formula VIII such as, for example, by treatment with dilute mineral acid.
• the compounds represented by Formula VIII wherein R is methyl or phenyl can, for example, also be prepared from camphor by reaction with a Grignard reagent represented by the formula wherein R is methyl or phenyl and X is a halogen atom.
• reaction product is hydrolyzed, dehydrated, and the dehydration product treated with glacial acetic acid in the presence of a strong acid such as, for example, sulfuric acid or hydrochloric acid, to yield the corresponding R -substituted isobornyl acetate.
• a strong acid such as, for example, sulfuric acid or hydrochloric acid
• Those compounds represented by Formula III wherein R in Formula 'V is a substituted phenyl group can be prepared, for example, by introducing, in a known manner, the desired substituent into an unsubstituted phenyl group of the corresponding acid amide and then hydrolyzing the amide.
• a nitro group can be introduced by nitrating with nitric acid.
• An amino group can be obtained in a known manner, such as by reducing the nitro group.
• a hydroxy group may be obtained from a methoxy group by treatment with, for example hydrobromic acid.
• the starting materials represented by Formula II are known compounds and can be prepared in a manner known in the art.
• the starting materials represented by Formula IV are new compounds and are within the scope of the present invention. These compounds can, for example, be prepared by the reduction of a compound represented by the Formula I. The reduction is preferably carried out catalytically utilizing a catalyst such as, for example, palladium/charcoal, platinum, Raney-nickel and the like.
• novel compounds represented by Formula I are therapeutically useful as amoebicides and bacteriostats, particularly against gram-negative bacteria such as, for example, Escherichia coli, Shigella sonnei or Shigella flexneri.
• oro-l,4-naphthoquinone has an LD of over 5000 mg./kg. p.o. and a CD of 4 mg./kg. p.o. against Escherichia coli, 8 mg./kg. p.o. against Slzigella flexneri and 7 nig/kg. p.o. against Shigella sonnei.
• ()-2'[(lR) 2 exo-bornylamino1-3- chloro-l,4-naphthoquinone has an LD of over 5000 mg./kg. p.o. and a CD of ca. 50 mg./kg. p.o. against Sltigella sonnei and Shigella flexneri.
• (+)-2-[(lR)-2endo-bornylaminol-3- bromo-l,4-naphthoquinone has an LD of over 5000 mg./kg. p.o. and a CD of ca. 50 mg./kg. p.o. against Shigella sonnei and Escherichia coli.
• mice were dewormed for 4 days. At the same time, they were placed on a carbohydrate-rich diet (popcorn). On the 5th day, no nourishment was administered. From the 6th day, until the end of the experiment they received drinking water which contained 4 g. of dihydrostreptomycin, 100 mg. of erythromycin and 400,000 units of mycostatin per litre. On the 6th day they again received popcorn. On the 7th day, once more no nourishment was administered.
• a piece of large intestine together with contents (ca. 200 mg.) was isolated and homogenized.
• Six different dilutions thereof were prepared as follows: 13 Amoco; $600,000; 4,000,000 and Anuoomoo- A drop from each dilution was streaked on an agar plate. After incubation for 48 hours, the number of colonies was counted and with the corresponding dilutions there was calculated the germ count per gram of piece of intestine for each mouse. By comparison of the individual germ counts for 5 mice with the average germ counts of 5 untreated mice there was calculated the percentage 6 germ reduction in each mouse. The results are stated in CD values.
• novel therapeutic agents represented by Formula I may be administered enterally or parenterally.
• a preferred mode of administration is orally in suitable pharmaceutical preparations such as, for example, drages, tablets, capsules and the like.
• suitable pharmaceutical preparations such as, for example, drages, tablets, capsules and the like.
• Such preparation preferably contain about 100, 200 or 250 mg. of active substance per dosage unit. It is contemplated that, in the case of adults, a daily dosage of up to 1000 mg. of active sub stance, corresponding to 14 mg./kg./day is administered in several divided doses. This dosage regimen may be adjusted by the clinician as the therapeutic situation requires.
• novel therapeutic agents of the present invention are administered enterally, i.e.. orally, or rectally. or parenterally in the form of pharmaceutical preparations which contain them in admixture with suitable pharmaceutical, organic or inorganic inert carrier materials which are suitable for such preparations.
• suitable pharmaceutical, organic or inorganic inert carrier materials include, for example, water, gelatin, lactose, starches, magnesium stearate, talc, vegetable oils, gums, polyalkylene glycols, petroleum jelly and the like.
• the pharmaceutical preparations can be in solid unit dosage form, e.g., in tablets, drages, suppositories, capsules or in liquid form, e.g., as solutions, suspensions or emulsions.
• Such preparations may be submitted to conventional pharmaceutical excipients such as, for example, sterilization and the like. They may also contain other therapeutically valuable substances or conventional pharmaceutical adjuvants such as preservatives, stabilizing agents, wetting agents, emulsifying agents, buffers and the like.
• EXAMPLE 1 A solution of 33.7 g. of rac.-2-endo-bornanarnine in 50 ml. of abs. alcohol were added dropwise with stirring at room temperature to a suspension of 22.7 g. of 2,3-dichloro-l,4-naphthoquinone in 200 ml. of abs. alcohol. After the addition, the reaction mixture was boiled at reflux for 4 hours, to form a dark red solution. The reaction mixture was then evaporated under reduced pressure, the residue taken up in 300 ml. of chloroform, the chloroform solution successively shaken out with ml. of water, three times with 100 ml. portions of 1 N hydrochloric acid and four times with 100 ml. portions of water.
• EXAMPLE 2 A suspension of 4.45 g. of 2,3-dichloro-l,4-naphthoquinone in 30 ml. of abs. benzene were treated with 2.226 g. of triethylamine. A solution of 3.218 g. of me.- 2-endo-bornanamine in 10 ml. of abs. benzene was then added dropwise with stirring over a period of 35 min. After stirring for 2 hours, the dark red colored suspension was filtered, the filtrate evaporated and the residue dissolved in methylene chloride. The resulting solution was washed successively with water, 1 N hydrochloric acid and water, dried over sodium sulfate, filtered and evaporated. The residue was treated in hexane with active charcoal and the rac.-2-(2-endo-bornylamino)-3-chloro-1,4- naphthoquinone crystallized as red crystals, MP. 109- 110.
• EXAMPLE 7 A suspension of 208.6 mg. 2-chloro-3-hydroxy-1,4-naphthoquinone in 5 ml. of abs. alcohol was treated with stirring at room temperature with 168.6 mg. of rac.-2-endobornanamine dissolved in 3 ml. of abs. alcohol. After stirring at room temperature for 60 minutes, the dark red solution was evaporated in vacuum, the residue treated with isopropyl ether and filtered. After evaporating off the mother liquor, the residue was chromatographed on 3.0 g. of kieselgel (0.2-0.5 mm.) with methylene chloride as the eluting agent. Fifteen fractions of 1 ml. each were collected. Fractions 5-12 contained rac.-2-(2-endo-bornylamino) 3 chloro 1,4-naphthoquinone which was crystallized [from methanol, M.P. 109-110.
• EXAMPLE 8 A total of 388.3 mg. of the product of Example 3(d), i.e., rac.-2 (2 endo bornylamino)-3 bromo-1,4-naphthoquinone, were heated to 100 with 848.0 mg. of lithium chloride in 50 ml. of abs. dimethylformamide. After 24 hours, the reaction mixture was concentrated to dryness, the residue taken up in ether and the solution washed with water, dried over sodium sulfate, filtered and evaporated. the residue crystallized from n-hexane to obtain rac.-2-(2- mm.) utilizing methylene chloride as the eluting agent.
• Oxygen gas was conducted through a solution of 100.0 mg. of rac.-2 (2 endo-bornylamino)-3-chloro-l,4-dihydroxy-naphthalene in 20 ml. of abs. alcohol for 2 hours. The red solution was thereafter evaporated in vacuum and the residue crystallized from n-hexane to obtain rac.-2-(2- endo-bornylamino) 3-chloro-1,4-naphthoquinone, M.P. 109111.
• EXAMPLE 1 A suspension of 11.35 g. of 2,3-dichloro-1,4-naphthoquinone in 100 ml. of abs. alcohol was treated, with stirring, over a period of 15 minutes with a solution of 16.73 g. of rac.-Z-endo-1,4,7,7-tetramethylnorbornanamine in 50 ml. of abs. alcohol. The resulting dark red solution was refluxed for two hours. The reaction mixture was thereafter evaporated under reduced pressure. The residue was dissolved in 200 ml. of methylene chloride and successively shaken out with 100 ml. of water, three times with 50 ml. portions of 1 N hydrochloric acid and three times with 100 ml.
• EXAMPLE 12 A suspension of 4.42 g. of 2,3-dichloro-l,4-naphthoquinone in 50 ml. of abs. alcohol was treated with 6.5 g. of rac. 2 exo-l,4,7,7-tetramethyl-norbornanamine in 50 ml. of abs. alcohol. The reaction mixture was then refluxed for 3 hours. The resulting dark red solution was evaporated and the residue dissolved in 100 ml. of methylene chloride, shaken out with 50 ml. of water, three times with 25 ml. portions of 3 N hydrochloric acid and four times with 50 ml. portions of water.
• EXAMPLE 13 A suspension of 4.54 g. of 2,3-dichloro-1,4-napthoquinone in 100 ml. methylene chloride were treated at room temperature with 4.45 g. triethylamine to form a browngreen suspension. To this mixture was added 5.564 g. of rac.-4-propyl-Z-exo-bornanamine hydrochloride and the reaction mixture maintained under reflux for 24 hours. Thereafter, the reaction mixture was worked up. The methylene chloride solution was successively shaken with water, with 1 N hydrochloric acid and again with water, dried over sodium sulfate, filtered and evaporated. The residue was recrystallized from alcohol.
• the rac. 4 propyl-2-exo-bornanamine hydrochloride utilized as the starting material can be obtained from the corresponding oxime in a manner analogous to that of Examples 11 and 12.
• EXAMPLE 14 A suspension of 2.27 g. of 2,3-dichloro-il,4naphthoquinone in 50 ml. of methylene chloride was treated at room temperature with 2.43 g. triethylamine. To the resulting brown green suspension was added 3.455 g. rac.-4- heptyl-Z-exo-bornanamine-hydrochloride and the mixture 1 1 boiled under reflux for 17 hours. The reaction mixture was then successively shaken out with water, 1 N hydrochloric acid and again with water, dried over sodium sulfate, filtered and evaporated.
• the rac. 4 heptyl-2-exo-bornanamine-hydrochloride starting material can be manufactured as follows:
• the reaction mixture was cooled by shaking with ice water and washed with 50 ml. of water and 200 ml. of 1:1 mixture of water and hydrochloric acid.
• the ether phase was then washed neutral with five 150 ml. portions of water, dried over sodium sulfate, filtered and evaporated.
• the residue (114.5 g.) was put under water vapor distillation and 1.8 liter of distillate was collected.
• the distillate was mixed with 300 ml. of ether, the phases separated and the ether phase washed three times with 150 ml. portions of water. dried under sodium sulfate, filtered and evaporated. There was obtained 71.4 g. rac.-2-heptynyl-2-borneol, B.P. 99100/0.01 mm. Hg.
• EXAMPLE 15 A solution of 2.3 g. of 2,3-dichloro-1,4-naphthoquinone in 50 ml. of methylene chloride was heated to reflux temperature and a second solution of 2.3 g. rac.-4- phenyl-Z-exo-bornanamine and 1.38 ml. triethylamine in 50 ml. methylene chloride was added dropwise over a period of minutes. After an hour, an additional 0.458 g. of rac.-4-phenyl-2-exo-bornanamine were added. After an additional 4 hours, the reflux was stopped and the mixture cooled, shaken three times with water, dried over sodium sulfate and evaporated in a vacuum.
• the rac.-4-phenyI-Z-exo-bornanamine used as the starting material can be produced from the corresponding oxime in an analogous manner to that of Examples 11 and 12.
• EXAMPLE 16 A solution of 2.6 g. rac.-4-phenethyl-2-exo-bornanamine and 1.38 ml. triethylamine in 50 ml. benzene was added dropwise to a solution of 2.3 g. 2,3-dichloro-1,4- naphthoquinone in 50 ml. benzene which was maintained at 50". After the addition was complete, the mixture was stirred at 60 for 24 hours and then an additional 0.51 g. rac.-4-phenethyl-2-exo-bornanamine was added and the mixture stirred for another 24 hours. The mixture was allowed to cool and then was shaken with water.
• the starting material i.e., rac.-4-(p-nitrophenyl)-2 exo-bornanamine, was obtained in the following manner:
• EXAMPLE 18 The following ingredients were homogeneously blended and filled into gelatin capsules utilizing a conventional capsule filling machine.
• Amount per Ingredient capsule, mg.
• Weight per Ingredient tablet, mg.
• R is hydrogen, halogen or lower alkoxy and R1 iS wherein R is hydrogen, lower alkyl, phenyl, substituted phenyl wherein the substituents are selected from the group consisting of halogen, nitro, amino and hydroxy or phenyl lower alkyl.
• R is chloro and R is 2-endo-bornyl, i.e., the compound rac.-Z-(2endo-hornylamino)-3-chloro 1,4 naphthoquinone.
• R is chloro and R is (1R)-2-endo-bornyl, i.e., the compound )-2-[(lR)-2-endo-bornylamino]-3-chloro-l,4- naphthoquinone.
• R is chloro and R is (lR)-2-exo-bornyl, i.e., the compound 2 [(lR) 2 exo-bornylamino]-3-chloro-1,4- naphthoquinone.
• R is bromo and R, is (lR)-2-endo-bornyl, i.e., the compound 2 1R) 2 endo-bornyl-amino]-3- bromo-1,4-naphthoquinone.
• R is bromo
• R is Z-endo-bornyl, i.e., the compound rac.- 2-(Z-endo-bornylamino)-3-brorno-1,4-naphthoquinone.
• R is hydrogen and R is Z-endo-bornylamino, i.e., the compound rac. 2 (2 endo-bornylamino) 1,4- naphthoquinone.
• R is chloro and R is Z-endo-norbornyl, i.e., the compound rac. 3 chloro 2 (2 endo-norbomylamino)-1,4- naphthoquinone.
• R is chloro and R is 2-exo-norbornyl, i.e., the compound rac. 3 chloro 2 (2 exo-norbornylamino)-1,4- naphthoquinone.
• R is chloro and R is 2-exo-bornyl, i.e., the compound 15 me. 2 (2 exo-bornylamino) 3 chloro 1,4- naphthoquinone.
• R is bromo and R is 2-exo-bornyl, i.e., the compound rac. 2 (2 eXo-bornylamino) 3 brorno 1,4- naphthoquinone.
• R is methoxy and R is 2-exo-bomyl, i.e., the compound rac. 2 (2 exo-bornylamino) 3 methoxy l,4- naphthoquinone.
• R is chloro and R is 2 endo 1,4,7,7-tetramethylnorbornyl, i.e., the compound rac. 3 chloro 2 [2- endo(l,4,7,7 tetramethylnorbornyl)-amino] 1,4- naphthoquinone.
• R is chloro and R is 2 exo 1,4,7,7-tetramethylnorbornyl, i.e., the compound rac. 3 chloro 2 [2- exo (l,4,7,7 tetramethylnorbornyl)amino] 1,4- naphthoquinone.
• R is chloro and R is 4 n-propyl-Z-exo-bornyl, i.e., the compound rac. 3 chloro 2 [(4 propyl 2 exobornyl -amino] -1,4-naphthoquinone.
• R is chloro and R is 4-n-heptyl-2-exo-bornyl, i.e., the compound rac. 3 chloro 2 [(4-hep-tyl-2-exo-bornyD- amino]-1,4-naphthoquinone.
• R is chloro and R is 4-phenyi-2-exo-bornyl, i.e., the compound rac. 3 chloro 2 [(4phenyl-2-exo-bornyl)- amino]-l,4-naphthoquinone.
• VIVIAN GARNER Primary Examiner US. Cl. X.R.

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Cited By (1)

• 1970
  • 1970-07-17 CH CH1090570A patent/CH548984A/xx not_active IP Right Cessation
• 1971
  • 1971-06-30 BG BG17939A patent/BG19587A3/xx unknown
  • 1971-07-05 ZA ZA714392A patent/ZA714392B/xx unknown
  • 1971-07-05 IL IL37228A patent/IL37228A/xx unknown
  • 1971-07-09 US US00162029A patent/US3729492A/en not_active Expired - Lifetime
  • 1971-07-13 CS CS515271A patent/CS157720B2/cs unknown
  • 1971-07-13 IE IE888/71A patent/IE35537B1/xx unknown
  • 1971-07-14 NL NL7109717A patent/NL7109717A/xx unknown
  • 1971-07-15 FR FR7125896A patent/FR2100926B1/fr not_active Expired
  • 1971-07-15 HU HUHO1394A patent/HU162585B/hu unknown
  • 1971-07-15 CA CA118,290A patent/CA983044A/en not_active Expired
  • 1971-07-15 BR BR4493/71A patent/BR7104493D0/pt unknown
  • 1971-07-16 ES ES393339A patent/ES393339A1/es not_active Expired
  • 1971-07-16 GB GB3347571A patent/GB1314118A/en not_active Expired
  • 1971-07-16 BE BE770109A patent/BE770109A/fr unknown
  • 1971-07-16 DE DE19712135712 patent/DE2135712A1/de active Pending
  • 1971-07-16 NO NO2739/71A patent/NO134208C/no unknown
  • 1971-07-16 AT AT471673*1A patent/AT321902B/de not_active IP Right Cessation
  • 1971-07-16 OA OA54306A patent/OA03901A/fr unknown
  • 1971-07-16 SE SE7109227A patent/SE377798B/xx unknown
  • 1971-07-16 AT AT620571A patent/AT317191B/de not_active IP Right Cessation
  • 1971-07-17 RO RO67704A patent/RO59593A/ro unknown
• 1974
  • 1974-12-30 MY MY8/74A patent/MY7400008A/xx unknown

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